U.S. patent application number 11/280311 was filed with the patent office on 2006-06-01 for aminoanthryl derivative-substituted pyrene compound and organic light-emitting device.
This patent application is currently assigned to CANON KABUSHIKI KAISHA. Invention is credited to Keiji Okinaka, Akihito Saitoh, Akihiro Senoo, Kazunori Ueno, Naoki Yamada, Masataka Yashima.
Application Number | 20060115678 11/280311 |
Document ID | / |
Family ID | 36567724 |
Filed Date | 2006-06-01 |
United States Patent
Application |
20060115678 |
Kind Code |
A1 |
Saitoh; Akihito ; et
al. |
June 1, 2006 |
Aminoanthryl derivative-substituted pyrene compound and organic
light-emitting device
Abstract
There is provided an aminoanthryl derivative-substituted pyrene
compound represented by the following general formula (1). ##STR1##
The compound is useful as a compound for an organic light-emitting
device exhibiting highly pure luminescent color, and an optical
output with high efficiency, high luminance, and long life.
Inventors: |
Saitoh; Akihito;
(Yokohama-shi, JP) ; Okinaka; Keiji;
(Kawasaki-shi, JP) ; Yamada; Naoki; (Tokyo,
JP) ; Yashima; Masataka; (Tokyo, JP) ; Senoo;
Akihiro; (Kawasaki-shi, JP) ; Ueno; Kazunori;
(Ebina-shi, JP) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
US
|
Assignee: |
CANON KABUSHIKI KAISHA
TOKYO
JP
|
Family ID: |
36567724 |
Appl. No.: |
11/280311 |
Filed: |
November 17, 2005 |
Current U.S.
Class: |
428/690 ;
313/504; 313/506; 428/917; 564/427; 564/433 |
Current CPC
Class: |
C07C 211/61 20130101;
H01L 51/0065 20130101; C09K 2211/1011 20130101; H01L 51/006
20130101; H01L 51/0068 20130101; C07C 217/94 20130101; C07C 2603/24
20170501; H01L 51/0067 20130101; Y10S 428/917 20130101; C07C
2603/50 20170501; C09K 2211/1007 20130101; C07C 211/54 20130101;
H01L 2251/308 20130101; C07C 217/92 20130101; C09K 2211/1014
20130101; C07C 2603/26 20170501; C09K 11/06 20130101; C07C 2603/74
20170501; H01L 51/0058 20130101; C07C 2603/18 20170501; H05B 33/14
20130101; H01L 51/0054 20130101; H01L 51/5012 20130101 |
Class at
Publication: |
428/690 ;
428/917; 313/504; 313/506; 564/427; 564/433 |
International
Class: |
H01L 51/54 20060101
H01L051/54; H05B 33/14 20060101 H05B033/14; C09K 11/06 20060101
C09K011/06; C07C 211/00 20060101 C07C211/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 26, 2004 |
JP |
2004-342463 |
Sep 21, 2005 |
JP |
2005-273622 |
Claims
1. An aminoanthryl derivative-substituted pyrene compound
represented by the following general formula (1): ##STR31## (In the
general formula (1): Ar.sub.1 and Ar.sub.2 each represent a group
selected from the group consisting of a substituted or
unsubstituted aryl group and a substituted or unsubstituted
heterocyclic group; Ar.sub.1 and Ar.sub.2 may each represent a
group bonded through a linking group; Ar.sub.1 and Ar.sub.2 may be
identical to or different from each other; Ar.sub.1 and Ar.sub.2
may be bonded to each other to form a ring; Z.sub.1 represents a
group selected from the group consisting of a direct single bond, a
substituted or unsubstituted alkylene group, a substituted or
unsubstituted alkenylene group, a substituted or unsubstituted
alkynylene group, a substituted or unsubstituted aralkylene group,
a substituted or unsubstituted arylene group, and a substituted or
unsubstituted divalent heterocyclic group; Z.sub.1 may represent a
group bonded through a linking group; X.sub.1 represents a group
selected from the group consisting of a direct single bond, a
substituted or unsubstituted arylene group, and a substituted or
unsubstituted divalent heterocyclic group; X.sub.1 may represent a
group bonded through a linking group; X.sub.2 represents a group
selected from the group consisting of a direct single bond, a
substituted or unsubstituted alkylene group, a substituted or
unsubstituted alkenylene group, a substituted or unsubstituted
alkynylene group, a substituted or unsubstituted aralkylene group,
a substituted or unsubstituted arylene group, and a substituted or
unsubstituted divalent heterocyclic group; X.sub.2 may represent a
group bonded through a linking group; R.sub.1 and R.sub.3 each
represent a group selected from the group consisting of a hydrogen
atom, a deuterium atom, a halogen atom, a substituted or
unsubstituted alkyl group, a substituted or unsubstituted aryl
group, a substituted or unsubstituted alkoxy group, and a
substituted or unsubstituted amino group; R.sub.1 and R.sub.3 may
be identical to or different from each other; R.sub.2 represents a
group selected from the group consisting of a hydrogen atom, a
deuterium atom, a halogen atom, a substituted or unsubstituted
alkyl group, a substituted or unsubstituted aralkyl group, a
substituted or unsubstituted alkenyl group, a substituted or
unsubstituted alkynyl group, a substituted or unsubstituted alkoxy
group, a substituted or unsubstituted sulfide group, a substituted
or unsubstituted amino group, a substituted or unsubstituted aryl
group, and a substituted or unsubstituted heterocyclic group; and
R.sub.2 may be identical to or different from each other when b is
in plural; and a represents an integer of 1 to 9; b represents an
integer of 1 to 4; c represents an integer of 1 to 8; m represents
an integer of 1 to 3).
2. The aminoanthryl derivative-substituted pyrene compound
according to claim 1, which is represented by the following general
formula (2). ##STR32##
3. The aminoanthryl derivative-substituted pyrene compound
according to claim 2, which is represented by the following general
formula (3). ##STR33##
4. The aminoanthryl derivative-substituted pyrene compound
according to claim 2, which is represented by the following general
formula (4). ##STR34##
5. The aminoanthryl derivative-substituted pyrene compound
according to claim 3, which is represented by the following general
formula (5): ##STR35## (In the general formula (5): R.sub.4 and
R.sub.5 each represent a group selected from the group consisting
of a hydrogen atom, a deuterium atom, a halogen atom, a substituted
or unsubstituted alkyl group, a substituted or unsubstituted aryl
group, a substituted or unsubstituted alkoxy group, and a
substituted or unsubstituted amino group; R.sub.4 and R.sub.5 may
be identical to or different from each other; d represents an
integer of 1 to 8; e and f each represent an integer of 1 to 5; and
Y represents a substituted or unsubstituted alkyl group).
6. The aminoanthryl derivative-substituted pyrene compound
according to claim 5, which is represented by the following general
formula (6) in which Y represents a tert-butyl group. ##STR36##
7. The aminoanthryl derivative-substituted pyrene compound
according to claim 1, which is represented by the following general
formula (7). ##STR37##
8. The aminoanthryl derivative-substituted pyrene compound
according to claim 7, which is represented by the following general
formula (8). ##STR38##
9. The aminoanthryl derivative-substituted pyrene compound
according to claim 7, which is represented by the following general
formula (9). ##STR39##
10. The aminoanthryl derivative-substituted pyrene compound
according to claim 8, which is represented by the following general
formula (10): ##STR40## (In the general formula (10): R.sub.4 and
R.sub.5 each represent a group selected from the group consisting
of a hydrogen atom, a deuterium atom, a halogen atom, a substituted
or unsubstituted alkyl group, a substituted or unsubstituted aryl
group, a substituted or unsubstituted alkoxy group, and a
substituted or unsubstituted amino group; R.sub.4 and R.sub.5 may
be identical to or different from each other; d represents an
integer of 1 to 8; e and f each represent an integer of 1 to 5; and
Y represents a substituted or unsubstituted alkyl group).
11. The aminoanthryl derivative-substituted pyrene compound
according to claim 10, which is represented by the following
general formula (11) in which Y represents a tert-butyl group.
##STR41##
12. The aminoanthryl derivative-substituted pyrene compound
according to claim 1, comprising at least one deuterium atom.
13. An organic light-emitting device comprising: a pair of
electrodes consisting of an anode and a cathode in which at least
one electrode is transparent or translucent; and a layer or a
plurality of layers each containing an organic compound and held
between the pair of electrodes, wherein at least one of the layers
each containing an organic compound contains at least one
aminoanthryl derivative-substituted pyrene compound according to
claim 1.
14. The organic light-emitting device according to claim 13,
wherein the layer containing at least one aminoanthryl
derivative-substituted pyrene compound comprises a light emission
layer.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an aminoanthryl
derivative-substituted pyrene compound, and to an organic
light-emitting device using the compound.
[0003] 2. Related Background Art
[0004] An organic light-emitting device is a device which includes
a thin film containing a fluorescent organic compound between an
anode and a cathode, which generates an exciton from the
fluorescent compound by injection of an electron and an electron
hole (hole) from each electrode, and which utilizes light to be
radiated when the exciton returns to a ground state.
[0005] In a study conducted by Eastman Kodak Company in 1987 (Appl.
Phys. Lett., 51, 913 (1987)), an anode formed of ITO, a cathode
formed of a magnesium-silver alloy, and an electron transport
material and a light-emitting material each formed of an aluminum
quinolinol complex are used. Further, there is reported light
emission of about 1,000 cd/m.sup.2 under application of a voltage
of about 10 V from a device having a function-separated two-layer
structure using a triphenylamine derivative as a hole transport
material. Related patent documents include U.S. Pat. No. 4,539,507,
U.S. Pat. No. 4,720,432, and U.S. Pat. No. 4,885,211.
[0006] Further, light emission in ultraviolet to infrared regions
is possible by changing the type of fluorescent organic compound.
Recently, various compounds have been studied actively (U.S. Pat.
No. 5,151,629, U.S. Pat. No. 5,409,783, U.S. Pat. No. 5,382,477,
Japanese Patent Application Laid-Open No. H02-247278, Japanese
Patent Application Laid-Open No. H03-255190, Japanese Patent
Application Laid-Open No. H05-202356, Japanese Patent Application
Laid-Open No. H09-202878, and Japanese Patent Application Laid-Open
No. H09-227576).
[0007] In addition to the organic light-emitting device using a low
molecular weight material as described above, an organic
light-emitting device using a conjugated polymer has been reported
by a group of Cambridge University (Nature, 347, 539 (1990)). In
this report, light emission has been confirmed from a single layer
of polyphenylene vinylene (PPV) formed in a coating system. Patents
related to an organic light-emitting device using a conjugated
polymer include U.S. Pat. No. 5,247,190, U.S. Pat. No. 5,514,878,
U.S. Pat. No. 5,672,678, Japanese Patent Application Laid-Open No.
H04-145192, and Japanese Patent Application Laid-Open No.
H05-247460.
[0008] Recently, an organic phosphorescence device using an iridium
complex such as Ir(ppy).sub.3 as a light-emitting material has
attracted attention and its high luminous efficiency has been
reported (Appl. Phys. Lett., 75, 4 (1999)).
[0009] Recent advances in organic light-emitting device are
remarkable and characteristics of the organic light-emitting device
allow formation of a thin and lightweight light-emitting device
with high luminance under application of a low voltage, wide range
of emission wavelengths, and high-speed response, thereby
suggesting the possibility of extensive uses. However, the organic
light-emitting device still has many problems in durability such as
change over long-term use, and degradation by an atmospheric gas
containing oxygen, by moisture, and the like. For application of
the organic light-emitting device to a full-color display or the
like, blue, green, and red light emissions with extended-life, high
conversion efficiency, and high color purity are required under the
present circumstances, and various proposals have been made.
[0010] An example of a material containing an anthracene ring used
for an organic light-emitting device is a phenylanthracene
derivative disclosed in Japanese Patent Application Laid-Open No.
H08-012600. In particular, use of a phenylanthracene derivative as
a blue light-emitting material or an electron-injection
transporting material allows formation of a favorable organic film
because of low crystallinity of the phenylanthracene derivative.
However, the phenylanthracene derivative has insufficient luminous
efficiency and durable life for practical use.
[0011] Japanese Patent Application Laid-Open No. H09-157643 and
Japanese Patent Application Laid-Open No. H10-072579 disclose an
aminoanthracene derivative and a diaminoanthracene derivative,
respectively. Those materials are used as light-emitting materials
and allow green light emission. However, devices produced by using
those materials each have low luminous efficiency and insufficient
durable life for practical use.
[0012] Japanese Patent No. 3008897 discloses a device using a
specific bianthryl compound as a light-emitting material, which
allows light emission with high luminance. However, the patent
document includes no description of luminous efficiency or durable
life.
[0013] Japanese Patent Application Laid-Open No. H11-008068
discloses a device using a specific anthracene compound containing
an olefin site as a light-emitting material, which allows yellow to
red light emissions. However, the device has insufficient luminous
efficiency for practical use.
[0014] Japanese Patent Application Laid-Open No. 2001-284050
discloses a device containing an anthracene derivative with a
specific structure, an electron transport compound, and another
fluorescent compound in a light-emitting medium layer, to thereby
provide a red light-emitting device with improved reliability.
However, the device has insufficient luminous efficiency for
practical use, and blue light emission is hardly observed because
of a device structure.
[0015] Japanese Patent Application Laid-Open No. 2002-324678
discloses an example of a material containing pyrene substituted
into a benzene ring used for an organic light-emitting device, to
thereby provide a device with favorable luminous properties and
durability. However, the device has low external quantum
efficiency, and the patent document includes no specific
description of durable life.
SUMMARY OF THE INVENTION
[0016] The present invention has been made in view of solving
problems in conventional art, and an object of the present
invention is therefore to provide a compound for an organic
light-emitting device exhibiting highly pure luminescent color, and
an optical output with high efficiency, high luminance, and long
life. Another object of the present invention is to provide an
organic light-emitting device which can be produced easily and at
relatively low cost.
[0017] The inventors of the present invention have conducted
extensive studies for attaining the above-mentioned objects, and
have completed the present invention.
[0018] That is, according to one aspect of the present invention,
there is provided an aminoanthryl derivative-substituted pyrene
compound represented by the following general formula (1): ##STR2##
(in the general formula (1): Ar.sub.1 and Ar.sub.2 each represent a
group selected from the group consisting of a substituted or
unsubstituted aryl group and a substituted or unsubstituted
heterocyclic group; Ar.sub.1 and Ar.sub.2 may each represent a
group bonded through a linking group; Ar.sub.1 and Ar.sub.2 may be
identical to or different from each other; Ar.sub.1 and Ar.sub.2
may be bonded to each other to form a ring;
[0019] Z.sub.1 represents a group selected from the group
consisting of a direct single bond, a substituted or unsubstituted
alkylene group, a substituted or unsubstituted alkenylene group, a
substituted or unsubstituted alkynylene group, a substituted or
unsubstituted aralkylene group, a substituted or unsubstituted
arylene group, and a substituted or unsubstituted divalent
heterocyclic group; Z.sub.1 may represent a group bonded through a
linking group;
[0020] X.sub.1 represents a group selected from the group
consisting of a direct single bond, a substituted or unsubstituted
arylene group, and a substituted or unsubstituted divalent
heterocyclic group; X.sub.1 may represent a group bonded through a
linking group;
[0021] X.sub.2 represents a group selected from the group
consisting of a direct single bond, a substituted or unsubstituted
alkylene group, a substituted or unsubstituted alkenylene group, a
substituted or unsubstituted alkynylene group, a substituted or
unsubstituted aralkylene group, a substituted or unsubstituted
arylene group, and a substituted or unsubstituted divalent
heterocyclic group; X.sub.2 may represent a group bonded through a
linking group;
[0022] R.sub.1 and R.sub.3 each represent a group selected from the
group consisting of a hydrogen atom, a deuterium atom, a halogen
atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted alkoxy
group, and a substituted or unsubstituted amino group; R.sub.1 and
R.sub.3 may be identical to or different from each other;
[0023] R.sub.2 represents a group selected from the group
consisting of a hydrogen atom, a deuterium atom, a halogen atom, a
substituted or unsubstituted alkyl group, a substituted or
unsubstituted aralkyl group, a substituted or unsubstituted alkenyl
group, a substituted or unsubstituted alkynyl group, a substituted
or unsubstituted alkoxy group, a substituted or unsubstituted
sulfide group, a substituted or unsubstituted amino group, a
substituted or unsubstituted aryl group, and a substituted or
unsubstituted heterocyclic group; and R.sub.2 may be identical to
or different from each other when b is in plural; and
[0024] a represents an integer of 1 to 9; b represents an integer
of 1 to 4; c represents an integer of 1 to 8; m represents an
integer of 1 to 3).
[0025] According to another aspect of the present invention, there
is provided an organic light-emitting device including: a pair of
electrodes consisting of an anode and a cathode in which at least
one electrode is transparent or translucent; and a layer or a
plurality of layers each containing an organic compound and held
between the pair of electrodes, in which at least one of the layers
each containing an organic compound contains at least one
aminoanthryl derivative-substituted pyrene compound.
[0026] The aminoanthryl derivative-substituted pyrene compound of
the present invention is a material for an organic light-emitting
device having multifunctional properties such as highly efficient
light emission and efficient electron and hole transport in a
molecule. The organic light-emitting device using the pyrene
compound of the present invention allows highly efficient light
emission under application of a low voltage. Further, change in
substituent of the pyrene compound can easily provide various
luminescent colors and excellent durability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 is a sectional view showing an example of an organic
light-emitting device according to the present invention;
[0028] FIG. 2 is a sectional view showing another example of the
organic light-emitting device according to the present
invention;
[0029] FIG. 3 is a sectional view showing still another example of
the organic light-emitting device according to the present
invention;
[0030] FIG. 4 is a sectional view showing yet another example of
the organic light-emitting device according to of the present
invention; and
[0031] FIG. 5 is a sectional view showing still yet another example
of the organic light-emitting device according to the present
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0032] Hereinafter, the present invention will be described more
specifically.
[0033] First, description will be given of an aminoanthryl
derivative-substituted pyrene compound of the present
invention.
[0034] The pyrene compound of the present invention can be used
mainly as a material for an organic light-emitting device. The
compound may be used for a light emission layer and used alone in
the light emission layer or used in a dopant (guest) material or a
host material, to thereby provide a device with high color purity,
high luminous efficiency, and long life.
[0035] For the pyrene compound of the present invention, molecular
design was performed for arranging an aminoanthryl derivative and a
pyrene derivative in consideration of providing multifunctional
properties such as highly efficient light emission and efficient
electron and hole transport in a molecule. For introduction of a
substituted amino group into an anthryl group for highly efficient
light emission and hole transport property, a HOMO/LUMO level of a
material may be adjusted by changing a substituent on the amino
group, to thereby change a luminescent color to luminescent colors
of blue, green light emission, and other colors at longer
wavelengths. Molecular design may be performed easily through
prediction of a HOMO/LUMO level by calculation in consideration of
difference in energy levels among a host material, a hole transport
layer, and an electron transport layer. The pyrene derivative is
most preferably substituted at a 1- or 4-position through synthesis
and shows high quantum efficiency. Further, improvement in carrier
transport property can be expected because of overlapping pyrene
rings. In addition, the introduction of the amino group on the
anthryl group may increase Tg, to thereby provide a material with
favorable thermal stability. Further, introduction of a bulky
substituent typified by a tert-butyl group into a pyrene ring and a
phenyl group on an amine allows suppression of cohesion between
molecules while appropriate carrier transport property is
maintained, to thereby improve the life of the device. In addition
to the above-mentioned consideration, the pyrene compound of the
present invention is designed in consideration of suppressing
molecular vibration by an isotope effect to suppress thermal
inactivation and has a deuterium atom-containing molecule unit
introduced thereinto. The pyrene compound of the present invention
is obtained through molecular design based on the consideration
described above, and the present invention has been completed.
[0036] For use of the pyrene compound of the present invention as a
dopant material, a concentration of the dopant with respect to a
host material is 0.01 wt % to 80 wt %, and preferably 1 wt % to 40
wt %. The dopant material may be included in an entire layer formed
of the host material uniformly or with a concentration gradient, or
may be partly included in a certain region of the layer of the host
material having a region containing no dopant material.
[0037] Examples of a substituted or unsubstituted alkyl group in
the general formula (1) include, but are not limited to: a methyl
group; a methyl-d1 group; a methyl-d3 group; an ethyl group; an
ethyl-d5 group; an n-propyl group; an n-butyl group; an n-pentyl
group; an n-hexyl group; an n-heptyl group; an n-octyl group; an
n-decyl group; an iso-propyl group; an iso-propyl-d7 group; an
iso-butyl group; a sec-butyl group; a tert-butyl group; a
tert-butyl-d9 group; an iso-pentyl group; a neopentyl group; a
tert-octyl group; a fluoromethyl group; a difluoromethyl group; a
trifluoromethyl group; a 2-fluoroethyl group; a
2,2,2-trifluoroethyl group; a perfluoroethyl group; a
3-fluoropropyl group; a perfluoropropyl group; a 4-fluorobutyl
group; a perfluorobutyl group; a 5-fluoropentyl group; a
6-fluorohexyl group; a chloromethyl group; a trichloromethyl group;
2-chloroethyl group; a 2,2,2-trichloroethyl group; a 4-chlorobutyl
group; a 5-chloropentyl group; a 6-chlorohexyl group; a bromomethyl
group; a 2-bromoethyl group; an iodomethyl group; a 2-iodoethyl
group; a hydroxymethyl group; a hydroxyethyl group; a cyclopropyl
group; a cyclobutyl group; a cyclopentyl group; a cyclohexyl group;
a cyclopentylmethyl group; a cyclohexylmethyl group; a
cyclohexylethyl group; a 4-fluorocyclohexyl group; a norbornyl
group; and an adamantyl group.
[0038] Examples of a substituted or unsubstituted aralkyl group
include, but are not limited to: a benzyl group; a 2-phenylethyl
group; a 2-phenylisopropyl group; a 1-naphthylmethyl group; a
2-naphthylmethyl group; a 2-(1-napthyl)ethyl group; a
2-(2-napthyl)ethyl group; a 9-anthrylmethyl group; a
2-(9-anthryl)ethyl group; a 2-fluorobenzyl group; a 3-fluorobenzyl
group; a 4-fluorobenzyl group; a 2-chlorobenzyl group; a
3-chlorobenzyl group; a 4-chlorobenzyl group; a 2-bromobenzyl
group; a 3-bromobenzyl group; and a 4-bromobenzyl group.
[0039] Examples of a substituted or unsubstituted alkenyl group
include, but are not limited to: a vinyl group; an allyl group (a
2-propenyl group); a 1-propenyl group; an iso-propenyl group; a
1-butenyl group; a 2-butenyl group; a 3-butenyl group; and a styryl
group.
[0040] Examples of a substituted or unsubstituted alkynyl group
include, but are not limited to: an acetylenyl group; a
phenylacetylenyl group; and a 1-propynyl group.
[0041] Examples of a substituted or unsubstituted aryl group
include, but are not limited to: a phenyl group; a phenyl-d5 group;
a 4-methylphenyl group; a 4-methoxyphenyl group; a 4-ethylphenyl
group; a 4-fluorophenyl group; a 4-trifluorophenyl group; a
3,5-dimethylphenyl group; a 2,6-diethylphenyl group; a mesityl
group; a 4-tert-butylphenyl group; a ditolylaminophenyl group; a
biphenyl group; a terphenyl group; a naphthyl group; a naphthyl-d7
group; an acenaphthylenyl group; an anthryl group; an anthryl-d9
group; a phenanthryl group; a phenanthryl-d9 group; a pyrenyl
group; a pyrenyl-d9 group; an acephenanthrylenyl group; an
aceanthrylenyl group; a chrysenyl group; a dibenzo chrysenyl group;
a benzoanthryl group; a benzoanthryl-d11 group; a dibenzoanthryl
group; a naphthacenyl group; a picenyl group; a pentacenyl group; a
fluorenyl group; a triphenylenyl group; a perylenyl group; and a
perylenyl-d11 group.
[0042] Examples of a substituted or unsubstituted heterocyclic
group include, but are not limited to: a pyrrolyl group; a pyridyl
group; a pyridyl-d5 group; a bipyridyl group; a methylpyridyl
group; a pyrimidinyl group; a pyrazinyl group; a pyridazinyl group;
a terpyrrolyl group; a thienyl group; a thienyl-d4 group; a
terthienyl group; a propylthienyl group; a benzothienyl group; a
dibenzothienyl group; a dibenzothienyl-d7 group; a furyl group; a
furyl-d4 group; a benzofuryl group; an isobenzofuryl group;
dibenzofuryl group; a dibenzofuryl-d7 group; a quinolyl group; a
quinolyl-d6 group; an isoquinolyl group; a quinoxalinyl group; a
naphthylidinyl group; a quinazolinyl group; a phenanthridinyl
group; an indolizinyl group; a phenazinyl group; a carbazolyl
group; an oxazolyl group; an oxadiazolyl group; a thiazolyl group;
a thiadiazolyl group; an acridinyl group; and a phenazinyl
group.
[0043] Examples of a substituted or unsubstituted aralkylene group
include, but are not limited to: a benzylene group; a
2-phenylethylene group; a 2-phenylisopropylene group; a
1-naphthylmethylene group; a 2-naphthylmethylene group; a
9-anthrylmethylene group; a 2-fluorobenzylene group; a
3-fluorobenzylene group; a 4-fluorobenzylene group; a
4-chlorobenzylene group; and a 4-bromobenzylene group.
[0044] Examples of a substituted or unsubstituted alkenylene group
include, but are not limited to: a vinylene group; an
iso-propenylene group; a styrylene group; and a
1,2-diphenylvinylene group.
[0045] Examples of a substituted or unsubstituted alkynylene group
include, but are not limited to, an acetylenylene group and a
phenyl acetylenylene group.
[0046] Examples of a substituted or unsubstituted arylene group
include, but are not limited to: a phenylene group; a biphenylene
group; a tetrafluorophenylene group; a dimethylphenylene group; a
naphthylene group; a phenanthrylene group; a pyrenylene group; a
tetracenylene group; a pentacenylene group; and a perylenylene
group.
[0047] Examples of a substituted or unsubstituted divalent
heterocyclic group include, but are not limited to: a furylene
group; a pyrrolylene group; a pyridylene group; a terpyridylene
group; a thienylene group; a terthienylene group; an oxazolylene
group; a thiazolylene group; and a carbazolylene group.
[0048] In a substituted or unsubstituted amino (--NR'R'') group,
examples of R' and R'' include, but are not limited to: a hydrogen
atom; a deuterium atom; the above-mentioned substituted or
unsubstituted alkyl group, aralkyl group, aryl group, or
heterocyclic group; an alkyl group, alkenyl group, alkynyl group,
aralkyl group, or amino group bonded through a substituted or
unsubstituted arylene group or divalent heterocyclic group; a
substituted silyl group; an ether group; a thioether group; and a
carbonyl group. Examples of the substituted or unsubstituted amino
group include, but are not limited to: an amino group; an
N-methylamino group; an N-ethylamino group; an N,N-dimethylamino
group; an N,N-diethylamino group; an N-methyl-N-ethylamino group;
an N-benzylamino group; an N-methyl-N-benzylamino group; an
N,N-dibenzylamino group; an anilino group; an N,N-diphenylamino
group; an N-phenyl-N-tolylamino group; an N,N-ditolylamino group;
an N-methyl-N-phenylamino group; an N,N-dianisolylamino group; an
N-mesityl-N-phenylamino group; an N,N-dimesitylamino group; an
N-phenyl-N-(4-tert-butylphenyl)amino group; and an
N-phenyl-N-(4-trifluoromethylphenyl)amino group.
[0049] Examples of a substituted or unsubstituted alkoxy group
include: an alkyloxy group or aralkyloxy group having the
above-mentioned substituted or unsubstituted alkyl group or aralkyl
group; and an aryloxy group having the above-mentioned substituted
or unsubstituted aryl group or heterocyclic group. Specific
examples thereof include, but are not limited to: a methoxy group;
an ethoxy group; a propoxy group; a 2-ethyl-octyloxy group; a
phenoxy group; a 4-tert-butylphenoxy group; a benzyloxy group; and
a thienyloxy group.
[0050] Examples of a substituted or unsubstituted sulfide group
include: an alkylsulfide group or aralkylsulfide group having the
above-mentioned substituted or unsubstituted alkyl group or aralkyl
group; and an arylsulfide group having the above-mentioned
substituted or unsubstituted aryl group or heterocyclic group.
Specific examples thereof include, but are not limited to: a
methylsulfide group; an ethylsulfide group; a phenylsulfide group;
and a 4-methylphenylsulfide group.
[0051] The term "a group bonded through a linking group" herein
employed refers to, for example, the "--Ph--O--Ph--" portion of
Exemplified Compound No. 17 of the representative examples of the
first compound as shown below, in which the ether group "--O--" is
a linking group.
[0052] Examples of a linking group bonding the above-mentioned
substituents include, but are not limited to: the above-mentioned
substituted or unsubstituted arylene group, divalent heterocyclic
group, alkylene group, alkenylene group, alkynylene group, or
aralkylene group; a substituted silyl group; an ether group; a
thioether group; and a carbonyl group.
[0053] Examples of a substituent which may be included in the
above-mentioned substituents and linking group include, but are not
limited to: a deuterium atom; an alkyl group or aralkyl group such
as a methyl group, an ethyl group, an n-propyl group, an n-butyl
group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an
n-octyl group, an n-decyl group, an iso-propyl group, an iso-butyl
group, a sec-butyl group, a tert-butyl group, an iso-pentyl group,
a neopentyl group, a tert-octyl group, a benzyl group, or a
2-phenylethyl group; an alkoxy group such as a methoxy group, an
ethoxy group, a propoxy group, a 2-ethyl-octyloxy group, a phenoxy
group, a 4-tert-butylphenoxy group, or a benzyloxy group; an aryl
group such as a phenyl group, a 4-methylphenyl group, a
4-ethylphenyl group, a 3-chlorophenyl group, a 3,5-dimethylphenyl
group, a triphenylamino group, a biphenyl group, a terphenyl group,
a naphthyl group, an anthryl group, a phenanthryl group, or a
pyrenyl group; a heterocyclic group such as a pyridyl group, a
bipyridyl group, a methylpyridyl group, a thienyl group, a
terthienyl group, a propylthienyl group, a furyl group, a quinolyl
group, a carbazolyl group, or an N-ethylcarbazolyl group; a halogen
group; a hydroxyl group; a cyano group; and a nitro group.
[0054] Preferred examples of the pyrene compound of the present
invention include: a compound in which Z.sub.1 represents a direct
single bond and m=1, that is, a compound represented by the
following general formula (2); a compound in which X.sub.2
represents a direct single bond, that is, a compound represented by
the following general formula (3) or (4); a compound represented by
the following general formula (5) in which a substituent is
introduced into at least a 7-position of the pyrene ring; and a
compound having a tert-butyl group as a steric hindrance group at a
7-position of the pyrene ring, that is, a compound represented by
the following general formula (6). ##STR3##
[0055] (In the general formulae: R.sub.4 and R.sub.5 each represent
a group selected from the group consisting of a hydrogen atom, a
deuterium atom, a halogen atom, a substituted or unsubstituted
alkyl group, a substituted or unsubstituted aryl group, a
substituted or unsubstituted alkoxy group, and a substituted or
unsubstituted amino group; R.sub.4 and R.sub.5 may be identical to
or different from each other;
[0056] d represents an integer of 1 to 8; and e and f each
represent an integer of 1 to 5).
[0057] A more preferred example of the pyrene compound of the
present invention is a compound in which Z.sub.1 represents a
phenylene group, that is, a compound represented by the following
general formula (7). A particularly preferred example of the pyrene
compound of the present invention is a compound in which Z.sub.1
represents a metaphenylene group, b=1, and m=1, that is, a compound
represented by the following general formula (8) or (9). Especially
preferred examples thereof include: a compound represented by the
following general formula (10) in which a substituent is introduced
into at least a 7-position of the pyrene ring; and a compound
having a tert-butyl group as a steric hindrance group at a
7-position of the pyrene ring, that is, a compound represented by
the following general formula (11). ##STR4##
[0058] (In the general formulae: R.sub.4 and R.sub.5 each represent
a group selected from the group consisting of a hydrogen atom, a
deuterium atom, a halogen atom, a substituted or unsubstituted
alkyl group, a substituted or unsubstituted aryl group, a
substituted or unsubstituted alkoxy group, and a substituted or
unsubstituted amino group; R.sub.4 and R.sub.5 may be identical to
or different from each other;
[0059] d represents an integer of 1 to 8; and e and f each
represent an integer of 1 to 5).
[0060] Specific examples of the substituted or unsubstituted alkyl
group, aryl group, alkoxy group, or amino group in the general
formulae (5), (6), (10), and (11) include those described for the
general formula (1).
[0061] Next, typical examples of the pyrene compound of the present
invention will be described. However, the pyrene compound of the
present invention is not limited to those compounds. ##STR5##
##STR6## ##STR7## ##STR8## ##STR9## ##STR10## ##STR11## ##STR12##
##STR13## ##STR14## ##STR15## ##STR16## ##STR17## ##STR18##
[0062] Next, an organic light-emitting device of the present
invention will be described in more detail.
[0063] The organic light-emitting device of the present invention
includes: a pair of electrodes consisting of an anode and a
cathode; and a layer or a plurality of layers each containing an
organic compound and held between the pair of electrodes. In the
organic light-emitting device, at least one of the layers each
containing an organic compound, preferably a light emission layer,
contains at least one pyrene compound of the present invention.
[0064] FIGS. 1 to 5 show preferred examples of the organic
light-emitting device of the present invention.
[0065] FIG. 1 is a sectional view showing an example of an organic
light-emitting device according to the present invention. As shown
in FIG. 1, the organic light-emitting device has a structure in
which an anode 2, a light emission layer 3, and a cathode 4 are
provided on a substrate 1 in the order given. The light-emitting
device used herein is useful in the case where the device itself
has hole transport property, electron transport property, and light
emission property or where compounds having the respective
properties are used in combination.
[0066] FIG. 2 is a sectional view showing another example of the
organic light-emitting device according to the present invention.
As shown in FIG. 2, the organic light-emitting device has a
structure in which the anode 2, a hole transport layer 5, an
electron transport layer 6, and the cathode 4 are provided on the
substrate 1 in the order given. A light-emitting substance is
useful in the case where a material having one or both of hole
transport property and electron transport property is used for each
layer, and the light-emitting substance is used in combination with
a non-illuminant hole transport substance or electron transport
substance. In this case, the light emission layer is formed of the
hole transport layer 5 or the electron transport layer 6.
[0067] FIG. 3 is a sectional view showing still another example of
the organic light-emitting device according to the present
invention. As shown in FIG. 3, the organic light-emitting device
has a structure in which the anode 2, the hole transport layer 5,
the light emission layer 3, the electron transport layer 6, and the
cathode 4 are provided on the substrate 1 in the order given. This
organic light-emitting device has separate carrier transport
function and light-emitting function. The device is used in
combination with compounds each having hole transport property,
electron transport property, or light emission property as
appropriate, thereby allowing substantial increase in freedom of
choice in material to be used. Further, various compounds having
different emission wavelengths can be used, thereby allowing
increase in variety of luminescent colors. Further, luminous
efficiency may be improved by efficiently trapping each carrier or
exciton in the light emission layer 3 provided in the middle of the
device.
[0068] FIG. 4 is a sectional view showing yet another example of
the organic light-emitting device according to the present
invention. FIG. 4 has a structure shown in FIG. 3 except that a
hole injection layer 7 is inserted into a side of the anode 2. This
structure is effective for improving adhesiveness between the anode
2 and the hole transport layer 5 or for improving hole injection
property, which is effective in lowering a voltage to be applied to
the device. In FIG. 4, the same reference numerals as those of FIG.
3 represent the same layers.
[0069] FIG. 5 is a sectional view showing still yet another example
of the organic light-emitting device according to the present
invention. FIG. 5 has a structure shown in FIG. 3 except that a
layer for blocking travel of a hole or exciton to a side of the
cathode 4 (a hole/exciton-blocking layer 8) is inserted between the
light emission layer 3 and the electron transport layer 6. This
structure uses a compound having an extremely high ionization
potential for the hole/exciton-blocking layer 8 and is effective
for improving luminous efficiency. In FIG. 5, the same reference
numerals as those of FIG. 3 represent the same layers.
[0070] However, FIGS. 1 to 5 each show a very basic device
structure, and the structure of the organic light-emitting device
using the pyrene compound of the present invention is not limited
to the structures shown FIGS. 1 to 5. For example, the organic
light-emitting device of the present invention may have any one of
various layer structures including: a structure in which an
insulating layer is provided at an interface between an electrode
and an organic layer; a structure in which an adhesive or
interference layer is provided; and a structure in which a hole
transport layer is composed of two layers with different ionization
potentials.
[0071] The pyrene compound of the present invention may be used for
any one of the structures shown in FIGS. 1 to 5.
[0072] In particular, an organic layer using the compound of the
present invention is useful as a light emission layer, an electron
transport layer, or a hole transport layer. In addition, a layer
formed through a vacuum deposition method, a solution coating
method, or the like is hardly crystallized and has excellent
stability over time.
[0073] In the present invention, the above-mentioned pyrene
compound of the present invention is particularly used as a
component of the light emission layer. The compound may be used in
combination with a known low molecular weight or polymer hole
transport compound, light emission compound, electron transport
compound, or the like as required.
[0074] Examples of the compounds will be shown below.
[0075] A preferred hole-injection transporting material has
excellent mobility for facilitating injection of a hole from an
anode and for transporting the injected hole to a light emission
layer. Examples of a low molecular weight or polymer material
having hole-injection transporting property include, but are not
limited to: a triarylamine derivative; a phenylenediamine
derivative; a triazole derivative; an oxadiazole derivative; an
imidazole derivative; a pyrazoline derivative; a pyrazolone
derivative; an oxazole derivative; a fluorenone derivative; a
hydrazone derivative; a stilbene derivative; a phthalocyanine
derivative; a porphyrin derivative; poly(vinylcarbazole);
poly(silylene); poly(thiophene); and other conductive polymers.
Specific examples thereof will be partly shown below. Low Molecular
Weight Hole-Injection Transporting Materials ##STR19## ##STR20##
##STR21## Polymer Hole Transport Materials ##STR22##
[0076] Examples of a material which is mainly involved in a
light-emitting function except the pyrene compound of the present
invention include, but are not limited to: a polycyclic condensed
aromatic compound (including a naphthalene derivative, a
phenanthrene derivative, a fluorene derivative, a pyrene
derivative, a tetracene derivative, a coronene derivative, a
chrysene derivative, a perylene derivative, a
9,10-diphenylanthracene derivative, or rubrene); a quinacridone
derivative; an acridone derivative; a coumarin derivative; a pyran
derivative; Nile red; a pyrazine derivative; a benzoimidazole
derivative; a benzothiazole derivative; a benzoxazole derivative; a
stilbene derivative; an organometallic complex (including: an
organic aluminum complex such as tris(8-quinolinolato)aluminum; or
an organic beryllium complex); and a polymer derivative (including
a poly(phenylene vinylene) derivative, a poly(fluorene) derivative,
a poly(phenylene) derivative, a poly(thienylene vinylene)
derivative, or a poly(acetylene) derivative). Specific examples
thereof will be partly shown below. Low Molecular Weight
Light-Emitting Materials ##STR23## Polymer Light-Emitting Materials
##STR24## Metal Complex Light-Emitting Materials ##STR25##
[0077] The electron-injection transporting material may be
arbitrarily selected from materials which facilitate injection of
an electron from a cathode and which have a function of
transporting the injected electron into a light emission layer. The
material is selected in consideration of, for example, the balance
with the mobility of a carrier of the hole transport material.
Examples of a material having electron-injection transporting
property include, but are not limited to, an oxadiazole derivative,
an oxazole derivative, a thiazole derivative, a thiadiazole
derivative, a pyrazine derivative, a triazole derivative, a
triazine derivative, a perylene derivative, a quinoline derivative,
a quinoxaline derivative, a fluorenone derivative, an anthrone
derivative, a phenanthroline derivative, and an organometallic
complex. Specific examples thereof will be partly shown below.
##STR26## ##STR27##
[0078] In the organic light-emitting device according to the
present invention, the layer containing the pyrene compound of the
present invention and layers containing other organic compounds are
each formed through the following method. A thin film is generally
formed through a vacuum deposition method, an ionized deposition
method, sputtering, plasma, or a known coating method (such as a
spin coating, dipping, casting, LB, or inkjet method) in which a
compound is dissolved in an appropriate solvent. In film formation
through a coating method, in particular, a film may be formed by
using a compound in combination with an appropriate binder
resin.
[0079] The binder resin may be selected from a wide variety of
binder resins. Examples of the binder resin include, but are not
limited to: a polyvinyl carbazole resin; a polycarbonate resin; a
polyester resin; a polyallylate resin; a polystyrene resin; an ABS
resin; a polybutadine resin; a polyurethane resin; an acrylic
resin; a methacrylic resin; a butyral resin; a polyvinyl acetal
resin; a polyamide resin; a polyimide resin; a polyethylene resin;
a polyethersulfone resin; a diallyl phthalate resin; a phenol
resin; an epoxy resin; a silicone resin; a polysulfone resin; and a
urea resin. One kind of binder resin may be used alone, or two or
more kinds thereof may be mixed and used as a copolymer. Further,
an additive such as a known plasticizer, antioxidant, or
ultraviolet absorber may be used in combination as required.
[0080] An anode material preferably has as large a work function as
possible, and examples thereof include: a metal element such as
gold, platinum, silver, copper, nickel, palladium, cobalt,
selenium, vanadium, or tungsten; an alloy thereof; and a metal
oxide such as tin oxide, zinc oxide, indium oxide, indium tin oxide
(ITO), or indium zinc oxide. Further, a conductive polymer such as
polyaniline, polypyrrole, polythiophene, or polyphenylene sulfide
may also be used. Each of those electrode materials may be used
alone, or two or more kinds thereof may be used in combination.
Further, the anode may have a single layer structure or a
multilayer structure.
[0081] Meanwhile, a cathode material preferably has as small a work
function as possible, and examples thereof include: a metal element
such as lithium, sodium, potassium, calcium, magnesium, aluminum,
indium, ruthenium, titanium, manganese, yttrium, silver, lead, tin,
or chromium; and an alloy thereof such as a lithium-indium alloy, a
sodium-potassium alloy, a magnesium-silver alloy, an
aluminum-lithium alloy, an aluminum-magnesium alloy, or a
magnesium-indium alloy. A metal oxide such as indium tin oxide
(ITO) may also be used. Each of those electrode materials may be
used alone, or two or more kinds thereof may be used in
combination. Further, the cathode may have a single layer structure
or a multilayer structure.
[0082] The substrate to be used in the present invention is not
particularly limited, but examples thereof include: an opaque
substrate such as a metallic substrate or a ceramics substrate; and
a transparent substrate such as a glass substrate, a quartz
substrate, or a plastic sheet substrate. In addition, the substrate
may have a color filter film, a fluorescent color converting filter
film, a dielectric reflection film, or the like for controlling
luminescent color.
[0083] Further, a protective layer or a sealing layer may be formed
on the produced device to prevent contact between the device and
oxygen, moisture, or the like. Examples of the protective layer
include: a diamond thin film; a film formed of an inorganic
material such as metal oxide or metal nitride; a polymer film
formed of a fluorine resin, polyparaxylene, polyethylene, a
silicone resin, a polystyrene resin, or the like; and a
photo-curable resin. Further, the device itself may be covered with
glass, an airtight film, a metal, or the like and packaged with an
appropriate sealing resin.
[0084] A thin film transistor (TFT) may be produced on a substrate,
and then the device of the present invention may be produced to be
connected to TFT.
[0085] Regarding the emission direction of a device, the device may
have a bottom emission structure (structure in which light is
emitted from a substrate side) or a top emission structure
(structure in which light is emitted from an opposite side of the
substrate).
[0086] Hereinafter, the present invention will be described more
specifically with reference to examples, but the present invention
is not limited to the examples.
EXAMPLE 1
Method of Producing Exemplified Compound No. 3
(1) Synthesis of Intermediate
(9-bromo-10-(1-pyrenyl)anthracene))
[0087] In a stream of nitrogen, 16.8 g (50 mmol) of
9,10-dibromoanthracene was dissolved in a deaerated mixed solvent
containing 300 ml of toluene and 200 ml of ethanol, and the whole
was stirred. Then, an aqueous solution of sodium carbonate prepared
by dissolving 10.6 g of anhydrous sodium carbonate in 100 ml of
water was added to the mixture, and 5.78 g (5 mmol) of
tetrakis(triphenylphosphine)palladium was added thereto. The
resulting solution was stirred in an oil bath heated to 50.degree.
C. 16.4 g (50 mmol) of
1-[4,4,5,5-tetramethyl-1,3,2-dioxaboranyl]pyrene dissolved in 100
ml of toluene was added dropwise to the solution. In a stream of
nitrogen, the resulting mixture was stirred under heating for about
4 hours in an oil bath heated to 80.degree. C. The temperature of
the reaction solution was returned to room temperature, and an
organic layer was separated by adding toluene, ethyl acetate, and
water. The organic layer was dried by using magnesium sulfate to
distill off the solvent. The resultant was purified by silica gel
column chromatography (toluene:heptane=1:3), to thereby obtain 20.6
g of 9-bromo-10-(1-pyrenyl)anthracene.
(2) Synthesis of Exemplified Compound No. 3
[0088] In a nitrogen atmosphere, 344 mg (1.53 mmol) of palladium
acetate and 1.86 g (6.12 mmol) of tri-o-tolylphosphine were
dissolved in 300 ml of xylene, and the whole was stirred at room
temperature for 15 minutes. After addition of 100 ml of xylene, 10
g (21.9 mmol) of 9-bromo-10-(1-pyrenyl)anthracene was added to the
mixture, and the whole was stirred for 5 minutes in an oil bath
heated to 50.degree. C. 4.39 g (26 mmol) of N,N-diphenylamine was
dissolved in 30 ml of xylene, and the resulting solution was added
dropwise into the mixture. Subsequently, 4.63 g (48.2 mmol) of
sodium tert-butoxide was added to the mixture. The mixture was
stirred under heating for about 5 hours in an oil bath heated to
130.degree. C. The temperature of the reaction solution was
returned to room temperature, and 100 ml of water was added to the
reaction solution, to thereby separate a water layer and an organic
layer. Then, the water layer was extracted with toluene and ethyl
acetate and dried together with the organic layer by using sodium
sulfate. The solvent was distilled off, and the residue was
purified by silica gel column chromatography (toluene:heptane=1:3),
to thereby obtain 8.7 g of Exemplified Compound No. 3.
EXAMPLES 2 TO 6
Methods of Producing Exemplified Compounds Nos. 1, 2, 6, 7, and
8
[0089] The following compounds were used instead of
N,N-diphenylamine. That is, Exemplified Compounds Nos. 1, 2, 6, 7,
and 8 were produced in the same manner as in Example 1 except that
N-(2-naphthyl)-N-phenylamine, N-(1-naphthyl)-N-phenylamine,
N-(9-phenanthryl)-N-phenylamine, N-(9-anthryl)-N-phenylamine, and
N-(1-pyrenyl)-N-phenylamine were used respectively.
EXAMPLE 7
Method of Producing Exemplified Compound No. 5
(1) Synthesis of Intermediate
(9-[N,N-bis(4-methylphenyl)amino]-10-bromoanthracene)
[0090] In a stream of nitrogen, 11.2 g (30 mmol) of
9-[N,N-bis(4-methylphenyl)amino]anthracene was dissolved in 100 ml
of dioxane, and the whole was stirred at room temperature. Then,
1.68 g (30 mmol) of potassium hydroxide dissolved in 3 ml of water
was added to the mixture dropwise. 5.75 g of bromine was added
thereto, and the whole was stirred for 30 minutes. A 5% aqueous
solution of sodium thiosulfate was added to the mixture, and the
whole was stirred for 1 hour. The product was filtrated and washed
with methanol. The product was recrystallized by using toluene, to
thereby obtain 11.3 g of
9-[N,N-bis(4-methylphenyl)amino]-10-bromoanthracene.
(2) Synthesis of Exemplified Compound No. 5
[0091] In a stream of nitrogen, the following compounds were
dissolved in a deaerated mixed solvent containing 80 ml of toluene
and 40 ml of ethanol, and the whole was stirred. That is, 2.5 g
(6.7 mmol) of 9-[N,N-bis(4-methylphenyl)amino]-10-bromoanthracene
and 2.75 g (8.38 mmol) of
1-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)pyrene were used. Then,
an aqueous solution of sodium carbonate prepared by dissolving 850
mg of anhydrous sodium carbonate in 20 ml of water was added
dropwise to the mixture. In a stream of nitrogen, the mixture was
stirred under heating for 1 hour in an oil bath heated to
50.degree. C., and 770 mg (0.67 mmol) of
tetrakis(triphenylphosphine)palladium was added thereto. The
resulting solution was stirred under heating for about 4 hours in
an oil bath heated to 80.degree. C. The temperature of the reaction
solution was returned to room temperature, and an organic layer was
separated by adding toluene, ethyl acetate, and water. The organic
layer was dried by using magnesium sulfate to distill off the
solvent. The resultant was purified by silica gel column
chromatography (toluene:heptane=1:3), to thereby obtain 22 g of
Exemplified Compound No. 5.
EXAMPLE 8
Method of Producing Exemplified Compound No. 4
[0092] 18 g of Exemplified Compound No. 4 was produced in the same
manner and on the same scale as those of Example 7 by using 13.7 g
(30 mmol) of 9-[N,N-bis(4-tert-butylphenyl)amino]anthracene.
EXAMPLES 9 TO 11
Methods of Producing Exemplified Compounds Nos. 12, 19, and 24
[0093] Exemplified Compounds Nos. 12, 19, and 24 were produced in
the same manner and under the same synthesis conditions as those of
Example 7 through a reaction between
9-[N,N-bis(4-methylphenyl)amino]-10-bromoanthracene and the
following compounds.
[0094] That is, Exemplified Compound No. 12 was produced by using
4,4,5,5-tetramethyl-1,3,2-dioxaborane derived from
1-bromo-7-tert-butyl-3-methylpyrene (synthesized in accordance with
Organic Preparations and Procedures International (1997), 29,
321-330).
[0095] Exemplified Compound No. 19 was produced by using
4,4,5,5-tetramethyl-1,3,2-dioxaborane derived from
1-bromopyrene-d9.
[0096] Exemplified Compound No. 24 was produced by using
4,4,5,5-tetramethyl-1,3,2-dioxaborane derived from
2-bromopyrene.
EXAMPLE 12
Method of Producing Exemplified No. 95
[0097] 2.1 g of Exemplified Compound No. 95 was produced in the
same manner and under the same synthesis conditions as those of
Example 7.
[0098] 2.1 g of Exemplified Compound No. 95 was produced through a
reaction between: 2 g (3.73 mmol) of
9-[N,N-bis(4-tert-butylphenyl)amino]-10-bromoanthracene; and 1.8 g
(4.52 mmol) of 4,4,5,5-tetramethyl-1,3,2-dioxaborane derived from
1-bromo-7-tert-butyl-3-methylpyrene.
[0099] 4,4,5,5-tetramethyl-1,3,2-dioxaborane can be obtained from
1-bromo-7-tert-butyl-3-methylpyrene.
[0100] Exemplified Compound No. 95 can be obtained through a
reaction between 2 g (3.73 mmol) of the former compound and 1.8 g
(4.52 mmol) of the latter compound.
EXAMPLE 13
Method of Producing Exemplified Compound No. 14
[0101] 10 g (21.9 mmol) of 9-bromo-10-(1-pyrenyl)anthracene was
synthesized in the same manner as in Example 1.
[0102] 14.5 g (32.9 mmol) of
1-[N-(4-methylphenyl)-N-(4-tert-butylphenyl)amino]-4-[4,4,5,5-tetramethyl-
-1,3,2-dioxaboranyl]benzene was prepared.
[0103] In a stream of nitrogen, both compounds were dissolved in a
deaerated mixed solvent containing 200 ml of toluene and 100 ml of
ethanol, and the whole was stirred.
[0104] Then, an aqueous solution of sodium carbonate prepared by
dissolving 5.2 g of anhydrous sodium carbonate in 50 ml of water
was added to the mixture. The resulting solution was stirred in an
oil bath heated to 50.degree. C., and 2.66 g (2.30 mmol) of
tetrakis(triphenylphosphine)palladium was added thereto. The
resulting solution was stirred under heating for about 5 hours in
an oil bath heated to 80.degree. C. The temperature of the reaction
solution was returned to room temperature, and an organic layer was
separated by adding toluene, ethyl acetate, and water. The organic
layer was dried by using magnesium sulfate to distill off the
solvent. The resultant was purified by silica gel column
chromatography (toluene:heptane=1:3), to thereby obtain 11 g of
Exemplified Compound No. 14.
EXAMPLE 14
Method of Producing Exemplified Compound No. 56
(1) Synthesis of Intermediate
(3-bromo-5-[9-(N,N-bis(4-methylphenyl)amino)-10-anthryl]toluene)
[0105] In a stream of nitrogen, 12.5 g (50 mmol) of
3,5-dibromotoluene was dissolved in a deaerated mixed solvent
containing 300 ml of toluene and 200 ml of ethanol, and the whole
was stirred.
[0106] Then, an aqueous solution of sodium carbonate prepared by
dissolving 10.6 g of anhydrous sodium carbonate in 100 ml of water
was added to the mixture, and 5.78 g (5 mmol) of
tetrakis(triphenylphosphine)palladium was added thereto. The
resulting solution was stirred in an oil bath heated to 50.degree.
C., and 20.9 g (50 mmol) of
9-(N,N-bis(4-methylphenyl)amino)anthryl-10-boronic acid dissolved
in 100 ml of toluene was added dropwise slowly into the solution.
In a stream of nitrogen, the resulting solution was stirred under
heating for about 4 hours in an oil bath heated to 80.degree. C.
The temperature of the reaction solution was returned to room
temperature, and an organic layer was separated by adding toluene,
ethyl acetate, and water. The organic layer was dried by using
magnesium sulfate to distill off the solvent. The resultant was
purified by silica gel column chromatography (toluene:heptane=1:3),
to thereby obtain 16.8 g of
3-bromo-5-[9-(N,N-bis(4-methylphenyl)amino)-10-anthryl]toluene.
(2) Synthesis of Exemplified Compound No. 56
[0107] 2.5 g (4.61 mmol) of
3-bromo-5-[9-(N,N-bis(4-methylphenyl)amino)-10-anthryl]toluene was
prepared.
[0108] Then, 1.89 g (5.76 mmol) of
1-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)pyrene was prepared.
[0109] In a stream of nitrogen, both compounds were dissolved in a
deaerated mixed solvent containing 80 ml of toluene and 40 ml of
ethanol, and the whole was stirred. Then, an aqueous solution of
sodium carbonate prepared by dissolving 916 mg of anhydrous sodium
carbonate in 20 ml of water was added dropwise to the mixture. In a
stream of nitrogen, the mixture was stirred for 1 hour in an oil
bath heated to 50.degree. C., and 533 mg (0.461 mmol) of
tetrakis(triphenylphosphine)palladium was added thereto. The
resulting solution was stirred under heating for about 4 hours in
an oil bath heated to 80.degree. C. The temperature of the reaction
solution was returned to room temperature, and an organic layer was
separated by adding toluene, ethyl acetate, and water. The organic
layer was dried by using magnesium sulfate to distill off the
solvent. The resultant was purified by silica gel column
chromatography (toluene:heptane=1:3), to thereby obtain 2.91 g of
Exemplified Compound No. 56.
EXAMPLES 15 TO 18
Methods of Producing Exemplified Compounds Nos. 69, 71, 75, and
78
[0110] Exemplified Compounds Nos. 69, 71, 75, and 78 were produced
in the same manner and under the same synthesis conditions as those
of Example 14 by using the following compounds instead of
1-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)pyrene.
[0111] That is, Exemplified Compound No. 69 was produced by using
1-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)pyrene-d9 derived from
1-bromopyrene-d9 (exemplified in Example 10).
[0112] Exemplified Compound No. 71 was produced by using
2-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)pyrene derived from
2-bromopyrene (exemplified in Example 11).
[0113] Exemplified Compound No. 75 was produced by using
1-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)-7-tert-butyl-3-methoxypyrene
derived from 1-bromo-7-tert-butyl-3-methoxypyrene (synthesized in
accordance with Organic Preparations and Procedures International
(1997), 29, 321-330).
[0114] Exemplified Compound No. 78 was produced by using
1-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)-7-tert-butyl-3-methylpyrene
shown in Example 9.
EXAMPLE 19
Method of Producing Exemplified Compound No. 57
[0115] 3,5-dibromo-tert-butylbenzene was synthesized by using
4-tert-butylaniline in accordance with a document (J. Am. Chem.
Soc. (1991), 113, 4238). Exemplified Compound No. 57 was produced
in the same manner and under the same synthesis conditions as those
of Example 13 by using 3,5-dibromo-tert-butylbenzene instead of
3,5-dibromotoluene.
EXAMPLE 20
Method of Producing Exemplified Compound No. 77
(1) Synthesis of Intermediate (3-bromo-5-(1-pyrenyl)toluene)
[0116] 3-bromo-5-(1-pyrenyl)toluene was synthesized under the same
conditions as those of Example 1. In a stream of nitrogen, 12.5 g
(50 mmol) of 3,5-dibromotoluene was dissolved in a deaerated mixed
solvent containing 300 ml of toluene and 200 ml of ethanol, and the
whole was stirred. Then, an aqueous solution of sodium carbonate
prepared by dissolving 10.6 g of anhydrous sodium carbonate in 100
ml of water was added to the mixture. Then, 5.78 g (5 mmol) of
tetrakis(triphenylphosphine)palladium was added thereto. The
resulting solution was stirred in an oil bath heated to 50.degree.
C. Then, 16.4 g (50 mmol) of
1-[4,4,5,5-tetramethyl-1,3,2-dioxaboranyl]pyrene dissolved in 100
ml of toluene was added dropwise slowly to the solution in three
separate portions. In a stream of nitrogen, the resulting solution
was stirred under heating for about 4 hours in an oil bath heated
to 80.degree. C. The temperature of the reaction solution was
returned to room temperature, and an organic layer was separated by
adding toluene, ethyl acetate, and water. The organic layer was
dried by using magnesium sulfate to distill off the solvent. The
resultant was purified by silica gel column chromatography
(toluene:heptane=1:3), to thereby obtain 10.2 g of
3-bromo-5-(1-pyrenyl)toluene.
(2) Synthesis of Exemplified Compound No. 77
[0117] 9.51 g (21.9 mmol) of
3-(1-pyrenyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaboranyl)-toluene
was obtained from 3-bromo-5-(1-pyrenyl)toluene. 17.4 g (32.9 mmol)
of 9-bromo-10-{4-[N,N-bis(4-methylphenyl)amino]phenyl}anthracene
was prepared. In a stream of nitrogen, both compounds were
dissolved in a deaerated mixed solvent containing 200 ml of toluene
and 100 ml of ethanol, and the whole was stirred. Then, an aqueous
solution of sodium carbonate prepared by dissolving 5.2 g of
anhydrous sodium carbonate in 50 ml of water was added to the
mixture. The solution was stirred in an oil bath heated to
50.degree. C., and 2.66 g (2.30 mmol) of
tetrakis(triphenylphosphine)palladium was added thereto. The
resulting solution was stirred under heating for about 5 hours in
an oil bath heated to 80.degree. C. The temperature of the reaction
solution was returned to room temperature, and an organic layer was
separated by adding toluene, ethyl acetate, and water. The organic
layer was dried by using magnesium sulfate to distill off the
solvent. The resultant was purified by silica gel column
chromatography (toluene:heptane=1:3), to thereby obtain 11 g of
Exemplified Compound No. 77.
EXAMPLE 21
[0118] An organic light-emitting device having the structure shown
in FIG. 3 was produced through the method described below.
[0119] Indium tin oxide (ITO) as the anode 2 was formed as a film
having a thickness of 120 nm on a glass substrate as the substrate
1 through a sputtering method, and the resultant was used as a
transparent conductive supporting substrate. The resulting
substrate was subjected to ultrasonic cleaning in acetone and
isopropyl alcohol (IPA) in the order given. Then, the substrate was
washed in boiling IPA and dried. The substrate was subjected to
UV/ozone cleaning to be used as a transparent conductive supporting
substrate.
[0120] A chloroform solution containing 0.2 wt % of a compound
represented by the following structural formula as a hole transport
material was prepared. ##STR28##
[0121] This solution was dropped onto the above-mentioned ITO
electrode and formed into a film on the ITO electrode through spin
coating at a revolving speed of 500 rpm for 10 seconds at first and
then at a revolving speed of 1,000 rpm for 1 minute. Then, the
whole was placed in a vacuum oven at 80.degree. C. and dried for 10
minutes, to thereby completely remove the solvent in the thin film.
The thus-formed hole transport layer 5 had a thickness of 25
nm.
[0122] Next, as the light emission layer 3, Exemplified Compound
No. 3 described above was deposited on the hole transport layer 5.
The resulting light emission layer 3 had a thickness of 20 nm. A
degree of vacuum during deposition was 1.0.times.10.sup.-4 Pa and a
film formation rate was 0.2 to 0.3 nm/second.
[0123] Further, as the electron transport layer 6,
bathophenanthroline (BPhen) was formed into a film having a
thickness of 50 nm through a vacuum deposition method. A degree of
vacuum during deposition was 1.0.times.10.sup.-4 Pa and a film
formation rate was 0.2 to 0.3 nm/second.
[0124] Next, lithium fluoride (LiF) was formed into a film having a
thickness of 0.5 nm on the organic layer described above through a
vacuum deposition method, and an aluminum film having a thickness
of 150 nm was formed thereon through a vacuum deposition method, to
thereby produce an electron-injection electrode (cathode 4). As a
result, an organic light-emitting device with the
electron-injection electrode (cathode 4) was produced. A degree of
vacuum during deposition was 1.0.times.10.sup.-4 Pa. A lithium
fluoride film formation rate was 0.05 nm/second, and an aluminum
film formation rate was 1.0 to 1.2 nm/second.
[0125] The obtained organic EL device was covered with a protective
glass and sealed with an acrylic resin binder in a dry air
atmosphere to prevent degradation of the device by adsorption of
moisture thereon.
[0126] Under application of a voltage of 4 V to the thus-obtained
device having the ITO electrode (anode 2) as a positive electrode
and the Al electrode (cathode 4) as a negative electrode, green
light emission with an emission luminance of 960 cd/m.sup.2 and a
luminous efficiency of 7.6 lm/W was observed.
[0127] Further, the voltage was applied to the device for 100 hours
while a current density was maintained at 3.0 mA/cm.sup.2 in a
nitrogen atmosphere, resulting in slight luminance degradation from
an initial luminance of 290 cd/m.sup.2 to a luminance of 275
cd/m.sup.2 after 100 hours.
COMPARATIVE EXAMPLE 1
[0128] An organic light-emitting device was produced in the same
manner as in Example 21 and was subjected to the same evaluation
except that the following comparative compound was used instead of
Exemplified Compound No. 3. ##STR29##
[0129] Under application of a voltage of 4 V, green light emission
with an emission luminance of 190 cd/m.sup.2 and a luminous
efficiency of 2 lm/W was observed. Further, the voltage was applied
to the device for 100 hours while a current density was maintained
at 3.0 mA/cm.sup.2 in a nitrogen atmosphere, resulting in extensive
luminance degradation from an initial luminance of 52 cd/m.sup.2 to
a luminance of 26 cd/m.sup.2 after 100 hours.
EXAMPLES 22 TO 25
[0130] Organic light-emitting devices were produced in the same
manner as in Example 21 and were subjected to the same evaluation
except that the compounds shown in Table 1 were used instead of
Exemplified Compound No. 3. Table 1 shows the results.
TABLE-US-00001 TABLE 1 Exemplified Applied Compound voltage
Luminance Efficiency Example No. (V) (cd/m.sup.2) (1 m/W) 22 2 4.0
910 7.1 23 19 4.0 1020 8.0 24 24 4.0 780 7.7 25 55 4.0 1270 10
EXAMPLE 26
[0131] An organic light-emitting device was produced in the same
manner as in Example 21 except that
2,9-bis[2-(9,9-dimethylfluorenyl)]phenanthroline was used for the
electron transport layer 6 and Exemplified Compound No. 5 was used
for the light emission layer 3.
[0132] Under application of a voltage of 4 V to the thus-obtained
device having the ITO electrode (anode 2) as a positive electrode
and the Al electrode (cathode 4) as a negative electrode, green
light emission with an emission luminance of 970 cd/m.sup.2 and a
luminous efficiency of 7.7 lm/W was observed.
EXAMPLES 27 TO 45
[0133] Organic light-emitting devices were produced in the same
manner as in Example 26 and were subjected to the same evaluation
except that the compounds shown in Table 2 were used instead of
Exemplified Compound No. 5. Table 2 shows the results.
[0134] The voltage was applied to the device produced in each of
Examples 28, 33, 39, and 44 for 100 hours while a current density
was maintained at 3.0 mA/cm.sup.2 in a nitrogen atmosphere,
resulting in slight luminance degradation: from an initial
luminance of 290 cd/m.sup.2 to a luminance of 280 cd/m.sup.2 after
100 hours in Example 28; from an initial luminance of 410
cd/m.sup.2 to a luminance of 390 cd/m.sup.2 after 100 hours in
Example 33; from an initial luminance of 650 cd/m.sup.2 to a
luminance of 635 cd/m.sup.2 after 100 hours in Example 39; and from
an initial luminance of 590 cd/m.sup.2 to a luminance of 570
cd/m.sup.2 after 100 hours in Example 44. TABLE-US-00002 TABLE 2
Exemplified Applied Compound voltage Luminance Efficiency Example
No. (V) (cd/m.sup.2) (1 m/W) 27 4 4.0 770 7.6 28 12 4.0 590 7.7 29
14 4.0 330 3.3 30 36 4.0 780 7.7 31 47 4.0 750 5.9 32 49 4.0 970
7.7 33 56 4.0 1360 10.7 34 57 4.0 1090 10.7 35 71 4.0 940 9.2 36 77
4.0 350 3.4 37 78 4.0 1100 10.8 38 91 4.0 1080 10.7 39 95 4.0 1350
11.2 40 96 4.0 1040 10.2 41 98 4.0 210 2.4 42 99 4.0 170 2.2 43 100
4.0 170 1.9 44 105 4.0 1180 11.0 45 107 4.0 1240 10.5
COMPARATIVE EXAMPLE 2
[0135] An organic light-emitting device was produced in the same
manner as in Example 26 and was subjected to the same evaluation
except that the following comparative compound was used instead of
Exemplified Compound No. 5. ##STR30##
[0136] Under application of a voltage of 4 V, blue light emission
with an emission luminance of 50 cd/m.sup.2 and a luminous
efficiency of 0.3 lm/W was observed. Further, the voltage was
applied to the device for 100 hours while a current density was
maintained at 10 mA/cm.sup.2 in a nitrogen atmosphere, resulting in
extensive luminance degradation from an initial luminance of 37
cd/m.sup.2 to a luminance of 16 cd/m.sup.2 after 100 hours.
[0137] This application claims priority from Japanese Patent
Application No. 2004-342463 filed on Nov. 26, 2004 and Japanese
Patent Application No. 2005-273622 filed Sep. 21, 2005, which are
hereby incorporated by reference herein.
* * * * *